New approaches in petroleomics by FT-MS employed in crude oils with different physicochemical characteristics

Orientadores: Marcos Nogueira Eberlin, Alberto Wisniewski JuniorTese (doutorado) - Universidade Estadual de Campinas, Instituto de QuímicaResumo: O estudo de óleos brutos com características físico-químicas intrínsecas, como por exemplo, elevada acidez, severo processo de emulsificação, densidade elevada, °API baixo, e elevada quantidade de gás e água de produção, tem apresentado os maiores desafios quando se busca a compreensão química à nível molecular dessa complexa matriz por técnicas analíticas, não sendo diferente para o campo da petroleômica, que tem utilizado técnicas de altíssima resolução e exatidão em espectrometria de massas visando o estudo de óleos brutos e seus derivados. No primeiro capítulo dessa tese, o trabalho descreve o estudo de óleos brutos com diferentes características físico-químicas no âmbito da petroleômica a partir de novas estratégias empregando APPI FT-ICR MS otimizado por planejamentos experimentais. Também foi realizado de forma inédita, o estudo de um óleo bruto contaminado a partir da técnica de IM-MS, sendo possível a resolução, separação e identificação de seus contaminantes e aditivos. No segundo capítulo, foi realizado o estudo de óleos brutos com diferentes °API e suas frações SARA a partir da técnica de FT-ICR MS em combinação com múltiplas técnicas de ionização, com ênfase na caracterização abrangente das frações de resinas e asfaltenos. Além disso, uma adaptação no fracionamento SARA foi proposta, e correlações entre os dados obtidos a nível molecular via FT-ICR MS e os valores de °API de diferentes óleos brutos e suas respectivas frações SARA foram investigadas. Os resultados mostraram que é possível correlacionar os dados à nível molecular e os diferentes °API independentemente se a análise é realizada no óleo bruto individual ou em suas frações de resinas e asfaltenos, e ainda, independente da técnica de ionização utilizada. O pré-fracionamento SARA e análises por FT-ICR MS utilizando diferentes técnicas de ionização, permitiu a caracterização das frações individuais, proporcionando uma redução da complexidade da amostra e uma caracterização química mais completa e seletiva dos componentes presentes no óleo brutoAbstract: The study of crude oils with intrinsic physicochemical characteristics, such as high acidity, severe emulsification process, high density, low API gravity, and high amount of gas and water production, has presented the greatest challenges when one aims to understand at the molecular level this complex mixture using analytical techniques. It has not been different for the field called petroleomics, which has used techniques with ultra-high resolution and mass accuracy in mass spectrometry for the study of crude oils and their derivatives. In the first chapter of this thesis, it is describes the study of crude oils with different physicochemical characteristics in the scope of petroleomics from new strategies employing APPI FT-ICR MS technique which was optimized by experimental design. We also have performed a study of a contaminated crude oil using the IM-MS technique, being possible to resolve, separate and identify their contaminants and additives. In the second chapter, the study of crude oils with different API gravities and their SARA fractions was done using FT-ICR MS technique in combination with multiple ionization techniques, with emphasis on the comprehensive characterization of resin and asphaltene fractions. In addition, an adaptation in the SARA fractionation was applied, and correlations between the data obtained at the molecular level via FT-ICR MS and the API gravities of different crude oils and their respective SARA fractions were investigated. The results showed that it is possible to correlate the data at the molecular level and the API gravities regardless of whether the analysis is performed on individual crude oil or their resin and asphaltenes fractions, and also, regardless of the employed ionization technique. The SARA fractionation and FT-ICR MS analysis using different ionization techniques allowed the characterization of the individual fractions, providing a reduction of the sample complexity and a more complete and selective chemical characterization of the components present in crude oilsDoutoradoQuimica AnaliticaDoutor em Ciências2013/19161-4FAPES

Petroleomics by ion mobility mass spectrometry: resolution and characterization of contaminants and additives in crude oils and petrofuels

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing crude oils and their contaminants, as well as petrofuels and their additives. Whereas direct analysis of a crude oil sample contaminated with demulsifiers by the classical ESI(+/-)-FTICR-MS petroleomic approach was unsatisfactory since it responds only with abundance and m/z, and ionization is impaired due to suppression of polar compounds of crude oil by additives likely used in petroleum industry, IM-MS enables mobility separation of ions, particularly of double bond equivalent (DBE) series for a giving CnX class providing separated spectra which are typical obtained either for the crude oil or the contaminants, even suffering of ion suppression or low ionization efficiency. The combination of improved IM resolution and high mass resolving power (40,000@400) of the QTOF instrument provides useful information on class (N, NO, NS, etc.), carbon number (C-n), and unsaturation (DBE) levels for crude oils, allowing one to infer geochemical properties from DBE trends that can be compared with IM-MS data. As demonstrated by results of gasoline samples with additives, the IM-MS system also allows efficient separation and characterization of additives and contaminants in petrofuels.Ion mobility-mass spectrometry (IM-MS), performed with exceptional resolution and sensitivity in a new uniform-field drift tube ion mobility quadrupole time-of-flight (IM-QTOF) instrument, is shown to provide a useful tool for resolving and characterizing71144504463FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [2013/19161-4]2013/19161-4sem informaçãosem informaçãoWe would like to thank the Fundação de Amparo a Pesquisa do Estado de São Paulo (FAPESP) for the scholarship awarded to J.M.S. (process number 2013/19161-4), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Conselho Nacional de Des

Comprehensive characterization of asphaltenes by fourier transform ion cyclotron resonance mass spectrometry precipitated under different n-alkanes solvents

CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOAsphaltenes are still problematic fractions and their composition is not fully unveiled as it relates to the original crude oil and the precipitation method. In this work, the composition of asphaltenes precipitated with n-heptane and n-pentane from ten c32210381046CAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOsem informação140382/2016-02013/19161-

Advanced aspects of crude oils correlating data of classical biomarkers and mass spectrometry petroleomics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)The complex geochemical characteristics of crude oils can provide important information on oil generation, such as the input of organic matter and their depositional environments, also supporting exploration, extraction, and production. This work reports the first organic geochemical evaluation of oils from the first commercial Brazilian onshore field (Carmopolis, Sergipe, Brazil) via both classical biomarkers and petroleomics data collected via ultrahigh-resolution and accuracy Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Gas chromatography/mass spectrometry (GC/MS) was used to characterize the oil composition in terms of n-alkane, isoprenoid, terpane, and sterane biomarkers, whereas either positive or negative electrospray ionization (ESI) and FT-ICR were used to profile the polar constituents of the oils. GC/MS revealed geochemical characteristics that classify the oil at different levels of thermal evolution and biodegradation. FT-ICR MS attributed molecular formulas to more than 3000 polar oil constituents, allowing geochemical parameters to be inferred mainly from the carbon number (Cn) and double bond equivalent (DBE) trends, along with the N and O-2 classes. The Dia27(S + R)/alpha alpha alpha C-27(S + R), % C-28, and % C-29 parameters and S/(S + R)alpha alpha alpha C-29, alpha beta beta(S + R)/alpha beta beta + alpha alpha alpha(S + R)C-29, and % C-27 biomarkers obtained from GC/MS were responsible to indicate similarity between samples, whereas N and O-2 classes provided the most distinction among the crude oil blends in terms of the level of biodegradation and thermal maturity.The complex geochemical characteristics of crude oils can provide important information on oil generation, such as the input of organic matter and their depositional environments, also supporting exploration, extraction, and production. This work reports31212081217FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOPETROBRASFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)2013/19161-4sem informaçãosem informação0050.0078683.12.

Comprehensive Characterization of Asphaltenes by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Precipitated under Different <i>n</i>‑Alkanes Solvents

Asphaltenes are still problematic fractions and their composition is not fully unveiled as it relates to the original crude oil and the precipitation method. In this work, the composition of asphaltenes precipitated with <i>n</i>-heptane and <i>n</i>-pentane from ten crude oils from the Sergipe-Alagoas Basin were assessed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) using five ionization procedures (electrospray ionization (ESI), ESI­(+) with formic acid, ESI(−) with ammonium hydroxide, and ESI(−) with tetramethyl­ammonium hydroxide, and atmospheric pressure photoionization (APPI), APPI­(+) and APPI(−)) in combination with a 7.2 T LTQ FT Ultra Thermo Fisher spectrometer. The purpose was to evaluate compositional differences between C5- and C7-asphaltenes according to the adopted ionization methodologies. Asphaltenes were compared as a function of heteroatomic composition and aromaticity. Chemometrics strategies were employed to evaluate the heteroatom classes of higher variation among the groups. Ions that were shared by the asphaltenes and the crude oils and between the ionization methods were also evaluated for similarity. Results showed that <i>n</i>-heptane asphaltenes are more aromatic than <i>n</i>-pentane asphaltenes, which in turn were found to be more acidic and to display a higher heteroatomic complexity. Principal component analysis and the evaluation of shared ions showed that APPI(±) is able to detected asphaltene ions directly from the whole crude oil. It was also found that the use of different ionization methods with and without additives is fundamental to obtain more comprehensive chemical profiles in terms of classes and their constituents for crude oils and their asphaltenes and that the specific <i>n</i>-alkane used to precipitate asphaltenes leads to different chemical profiles

Sacha Inchi (plukenetia Volubilis L.) Oil Composition Varies With Changes In Temperature And Pressure In Subcritical Extraction With N-propane

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Sacha inchi is an oilseed crop that shows high oil content and it is an excellent source of polyunsaturated fatty acids. Temperature and pressure can influence in lipid composition on the subcritical extraction with n-propane. The highest extraction yield obtained was 30% under the conditions of 60 degrees C and 12 MPa. The extracted oil presented 442 mg of fatty acid g(-1) in terms of alpha linolenic acid. Analysis by easy ambient sonic-spray ionization mass spectrometry showed a typical TAG (Triacylglycerols) profile for Sacha inchi oil with major ions of m/z (mass-to-charge ratio) 895 (ALA-ALA-ALA), 897 (ALA-ALA-LA), 899 (ALA-LA-LA) and 901 (LA-LA-LA or OL-LA-ALA) in a form of adduct of [TAG + Na](+), in which ALA is alfa linoleic acid, LA is linoleic acid and OL is oleic acid. The phytosterols content (86.39-101.92 mg 100g(-1) of total lipids) varied according to the conditions applied for the n-propane extraction. In general, the subcritical fluid extraction with n-propane was found to preserve the important Sacha inchi oil bioactive constituents, that is, fatty acids, triacylglycerols and phytosterols. Regression analysis also showed that higher temperatures and pressures result in higher yields of phytosterols. (C) 2016 Elsevier B.V. All rights reserved.876470CapesSao Paulo Research Foundation (FAPESP) [2013/19161-4]Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP